CN103547639B - Active ray-curable inkjet ink and image forming method - Google Patents
Active ray-curable inkjet ink and image forming method Download PDFInfo
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- CN103547639B CN103547639B CN201280020052.4A CN201280020052A CN103547639B CN 103547639 B CN103547639 B CN 103547639B CN 201280020052 A CN201280020052 A CN 201280020052A CN 103547639 B CN103547639 B CN 103547639B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/34—Hot-melt inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet (AREA)
Abstract
Even if the present invention provides a kind of image that can also be stably formed fine under high-speed record, the active ray-curable inkjet ink good to the adaptability of various recording materials or use its image forming method.Described active ray-curable inkjet ink contains gellant, photopolymerizable compound and light trigger, collosol and gel phase in version is reversibly carried out by temperature, wherein, the quality that (1) is overall relative to ink has 3～14-CH containing molecular weight in the range of 300～1500 and in intramolecular in the range of 30～70 mass %2-CH2(methyl) acrylate compounds of construction unit shown in-O-is as described first photopolymerizable compound；(2) quality overall relative to ink in the range of 10～40 mass % containing (methyl) acrylate compounds that molecular weight is in the range of 300～1500 and ClogP value is in the range of 4.0～7.0 as described second photopolymerizable compound；And the total carbon atom number of (3) described gellant is more than 12, and the straight or branched alkyl chain containing carbon number more than 3.
Description
Technical field
The present invention relates to a kind of containing gellant and the active ray-curable of active ray solidification compound
Jetted ink and use its image forming method.
Background technology
In the past, ultraviolet or electron beam isoreactivity energy line is utilized to carry out the active ray-curable group solidified
Compound is at the coating of plastics, paper, woodwork and inorganic material etc., bonding agent, printing-ink, printing electricity
The various uses such as road plate and electric insulation Related product are practical.
It addition, the ink for inking system employing these polymerizable composition, polymerizable compositions includes utilizing ultraviolet (following
Referred to as " the UV ") uv-curing type ink jet ink solidified.Employ the ink-jet of this ultraviolet curing ink
Mode, owing to having rapid-drying properties, can carry out record on the recording materials do not have ink absorption, therefore,
The most just receive much concern.
But, in utilizing the image forming method of ink-jet system of these ultraviolet hardenings, at a high speed
(such as, if line recording mode, then recording materials transporting velocity is more than 30m/s to record；If
(shuttle back and forth) continuously recording mode, then print speed printing speed is 50m2/ more than hr) time, there is adjacent ink dot and merge,
The problem of image quality deterioration.
Any recording materials kind can be carried out ink mist recording, and prevents from becoming problem during ink mist recording
The known UV curable ink containing gellant of technology of " adjacent point merges " is (with reference to patent documentation
1～3).
Such as, Patent Document 1 discloses a kind of spray with oily gellant and photopolymerizable compound
Ink ink, discloses cationically polymerizable compound or free-radical polymerised compound as optical polymerism
Compound.
It addition, Patent Document 2 discloses one have curable monomer, gellant, in intramolecular
Having the side chain polymer of light-initiated part and the phase change ink of colorant, curable monomer discloses free radical
Polymerizable compound.
Patent Document 3 discloses one there is Chinese white, curable monomer, gellant and light to draw
Sending out the phase change ink of agent, curable monomer discloses free-radical polymerised compound.
But, in ink composite disclosed in these patent documentations 1～3, as above high
During speed recording, the suppression merging ink dot is the most insufficient.Additionally, there are ejection stability insufficient, nothing
The problem that method repeatability forms high resolution image well.
It addition, general UV curable ink is by using the relatively low molecule disclosed in patent documentation 1～3
The simple function of amount and two sense free-radical polymerised compounds, as polymerizable compound, prevent due to UV
Image film cracking such problem when cure shrinkage during irradiation causes printed article bending or bends printed article.
But, in there is the ink of gellant and photopolymerizable compound, it is less than 300 using molecular weight
In the case of the free-radical polymerised compound of lower molecular weight, there is also following problem: can spray
At a temperature of ink composite stability is insufficient, the stink of the stink of ink itself, printed article after solidification
Problem in the environmental health such as strong.
As the technology suppressing cure shrinkage in the case of not damaging curable, it is known to use such as patent literary composition
Offer the polymerism chemical combination in intramolecular with more than the trifunctional of oxirane (EO) unit disclosed in 1
Thing.But, if more use intramolecular more have the trifunctional of oxirane (EO) unit with
On multifunctional polymerizable compound, then the hydrophilic that ink is overall becomes the highest.Accordingly, it is difficult to make
Gellant is stably present in the ink that hydrophilic is high, therefore meets high image quality, curable, solidification receipts
The uv-curing type ink jet ink compositions of contracting full terms is the most still unaware of.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-126507 publication
Patent documentation 2: No. 2009/0046134 description of U.S. Patent Application Publication No.
Patent documentation 3: No. 2009/0038506 description of U.S. Patent Application Publication No.
Summary of the invention
Invent problem to be solved
The present invention completes with situation in view of the above problems, and it solves the technical problem that and is, it is provided that
Even if a kind of image that can also be stably formed fine under high-speed record, to various recording materials
The active ray-curable inkjet ink that adaptability is good.Use this active ray solid additionally, it is provided that a kind of
The image forming method of change type jetted ink.
In order to solve the scheme of problem
The above-mentioned technical problem of the present invention can be solved by following scheme.
[1] a kind of active ray-curable inkjet ink, its contain gellant (ゲ Le, gelating agent),
Photopolymerizable compound and light trigger, it reversibly carries out collosol and gel phase in version according to temperature, its
In,
(1) quality overall relative to ink, containing the molecular weight in the range of 30～70 mass % 300～
In the range of 1500 and in intramolecular, there are 3～14 (-CH2-CH2-O-) shown in (the first of construction unit
Base) acrylate compounds, as described first photopolymerizable compound,
(2) quality overall relative to ink, containing the molecular weight in the range of 10～40 mass % 300～
In the range of 1500 and ClogP value (methyl) acrylate compounds in the range of 4.0～7.0, as
Described second photopolymerizable compound, and,
(3) total carbon atom number of described gellant is more than 12, and is the straight chain of more than 3 containing carbon number
Or branched alkyl chain.
[2] the active ray-curable inkjet ink as described in [1], wherein, described active ray-curable sprays
Ink ink is possibly together with colorant.
[3] the active ray-curable inkjet ink as described in [1] or [2], wherein, described second optical polymerism
Compound is at least one (methyl) acrylate compounds in following (4) and (5),
(4) in intramolecular, there are 3～14 (-C (CH3)H-CH2-O-) shown in construction unit trifunctional with
On (methyl) acrylate compounds,
(5) there is (methyl) acrylate compounds of more than two senses of circulus in intramolecular.
[4] the active ray-curable inkjet ink as according to any one of [1]～[3], wherein, described gelling
Agent is at least one compound in the compound shown in following formula (G1) and (G2),
Formula (G1): R1-CO-R2
Formula (G2): R3-COO-R4
[in formula, R1～R4Separately represent that there is the linear fraction that carbon number is 3～36, and can
To have the alkyl chain of side chain].
[5] a kind of image forming method, it uses the active ray-curable spray according to any one of [1]～[4]
Ink ink, wherein, by described active ray-curable inkjet ink land recording materials when the recording materials
Temperature control at the collosol and gel phase transition temperature-20 of described active ray-curable inkjet ink～colloidal sol
In the range of gel phase transition temperature-10 DEG C.
Invention effect
By the said method of the present invention, it is possible to provide landform can also be stablized under high-speed record even if a kind of
Become fine image, the active ray-curable inkjet ink good to the adaptability of various recording materials.
Additionally, it is possible to provide a kind of image forming method using this active ray-curable inkjet ink.
That is, by the method for the present invention, it is possible to provide can also be stably (heavy under high-speed record even if a kind of
Existing property is good) suppression " merging of adjacent ink dot ", there is not ejection stability problem, low odor, and UV
Curable is good, and there is not the active ray-curable inkjet ink of cure shrinkage problem.It addition,
A kind of image forming method using this active ray-curable inkjet ink can be provided.
Accompanying drawing explanation
Fig. 1 is the figure of an example of the composition of the major part representing ink-jet recording apparatus
Detailed description of the invention
The active ray-curable inkjet ink of the present invention (hereinafter referred to as " jetted ink ", or referred to as " oil
Ink ") containing gellant, photopolymerizable compound, light trigger, preferably possibly together with colorant.The work of the present invention
Property ray-curable inkjet ink is characterised by, reversibly carries out collosol and gel phase in version according to temperature,
And meet whole important documents of above-mentioned (1)～(3).This feature is that first aspect is common to the invention of the 5th aspect
Technical characteristic.
From the viewpoint of the effect showing the present invention, the preferred above-mentioned ClogP of embodiments of the present invention
Value (methyl) acrylate compounds in the range of 4.0～7.0 is at least one in above-mentioned (4) and (5)
(methyl) acrylate compounds.And then, the most above-mentioned gellant is shown in above-mentioned formula (G1) and (G2)
At least one compound in compound.
Use the image that the image forming method of the active ray-curable inkjet ink of the present invention is preferably as follows
Forming method: by above-mentioned active ray-curable inkjet ink land temperature of recording materials when the recording materials
Degree controls to coagulate at collosol and gel phase transition temperature-20～this colloidal sol of above-mentioned active ray-curable inkjet ink
In the range of glue phase transition temperature-10 DEG C.
Hereinafter, the present invention, its element and being used for is implemented embodiments of the present invention, implements shape
State is described in detail.It should be noted that in this application, use "～" time meaning be to comprise it
Numerical value described front and back is as lower limit and higher limit.It addition, " (methyl) acrylate compounds " refers to
Methacrylate or acrylate compounds.
<ink composite>
The ink composite that the active ray-curable inkjet ink of the present invention is used is characterised by, extremely
Contain gellant, photopolymerizable compound and light trigger less, preferably possibly together with colorant.
It addition, above-mentioned active ray-curable inkjet ink is characterised by, reversibly enter according to temperature
Row collosol and gel phase in version, and meet whole following important document (1)～(3).
(1) quality overall relative to ink, containing the molecular weight in the range of 30～70 mass % 300～
In the range of 1500 and in intramolecular, there are 3～14 (-CH2-CH2-O-) shown in (the first of construction unit
Base) acrylate compounds, as above-mentioned first photopolymerizable compound,
(2) quality overall relative to ink, containing the molecular weight in the range of 10～40 mass % 300～
In the range of 1500 and ClogP value (methyl) acrylate compounds in the range of 4.0～7.0, as
Above-mentioned second photopolymerizable compound.
(3) total carbon atom number of above-mentioned gellant is more than 12, and is the straight chain of more than 3 containing carbon number
Or branched alkyl chain.
Here, so-called " LogP value " be expression organic solvent to the organic compound of water and 1-capryl alcohol affine
The coefficient of property.1-Octanol/water Partition Coefficients P is that the compound of trace dissolves in the pungent alcohol and water of 1-as solute
Partition equilibrium during two liquid phase solvents, is the ratio of the equilibrium concentration of compound in each solvent, uses they phases
Logarithm LogP for the end 10 represents.That is, so-called " logP value " is partition coefficient right of 1-octanol/water
Numerical value, it is known that it is the important parameter of the hydrophilic and hydrophobic representing molecule.
So-called " CLogP value " is the LogP value by being calculated by.CLogP value can pass through fragment method, former
Son calculates close to method (atom approach) etc..More specifically, in order to calculate ClogP value, it is possible to use
Document (C.Hansch and A.Leo, " Substituent Constants for Correlation Analysis in
Chemistry and Biology " (John Wiley&Sons, New York, 1969)) fragment method recorded or
Following commercially available software kit 1 or 2.
Software kit 1:MedChem Software (Release3.54, in August, 1991, Medicinal
Chemistry Project, Pomona College, Claremont, CA)
Software kit 2:Chem Draw Ultra ver.8.0. (in April, 2003, CambridgeSoft
Corporation, USA)
Numerical value in the ClogP value described in present specification etc. is to use software kit 2 to calculate
" ClogP value ".
Hereinafter, the various compounds etc. of the active ray-curable inkjet ink constituting the present invention are carried out in detail
Thin explanation.
(gellant)
The gellant of the present invention is the compound that can make ink composite reversibly gelation.
So-called gel refers to: the macromolecule mesh that due to layer structure, formed by non-covalent bond or hydrogen bond,
The macromolecule mesh that formed by physical property state of aggregation, the interaction of coherent structure etc. of microgranule, precipitation
The interaction etc. of micro-crystallization, and the structure making material lose self-movement and assembling.It addition, it is so-called
Gelation refers to solidify with the steeply rising of viscosity, elastic increasing, semi-solid preparation or thickening.
In this application, what is called " reversibly carrying out collosol and gel phase in version according to temperature " refers to: due to
Variations in temperature and high in low viscosity and mobility and show liquidus behavior colloidal sol (sol) state and viscosity is high and
The most reversibly carry out changing (conversion) between display solid-state or gel (gel) state of semisolid character.
It addition, so-called " collosol and gel phase transition temperature ", refer to that changing (transformation) from collosol state is gel
The temperature that the change (transformation) of state is put.Be referred to as gel transition temperature, gel solution temperature, gel soften
Temperature, sol-gel transition point, gelation point explicans identical.
The sol-gel transition temperature of the present invention can at random set, but from the stable injection of ink,
The viewpoints such as harm produced by high-temperature heating consider, preferably in the range of 30～100 DEG C.It addition, colloidal sol
Gel transition temperature is preferably between the ink temperature in ink jet recording head and the temperature of recording materials.
The assay method of above-mentioned sol-gel transition temperature such as can place gelatinous test on hot plate
Sheet also heats hot plate, and the temperature of determination test plate shape collapse, as collosol and gel phase transition temperature
Obtain.Further, it is possible to use the commercially available determination of viscoelasticity device (viscoelastic that such as, Physica company manufactures
Property determinator MCR300) it is measured.
Sol-gel transition temperature can according to the kind of gellant described later, photopolymerizable compound etc., add
Dosages etc. are adjusted.
Generally important document necessary to gelation, i.e. the structure that gellant must possess is to have hydrophobicity concurrently
Portion's (such as carbon number is the alkyl chain of 3～36) and hydrophilic portion (such as polar group).The temperature of ink
Degree decline, as solvent polymerizable compound molecular motion reduce time, hydrophobicity portion passes through molecular separating force
Surround solvent while assembling, and hydrophilic portion assembles each other by hydrogen bond, is consequently formed gel.
Therefore, for stable ejection or no matter how print speed printing speed can stably suppress ink dot to merge,
Guarantee that the compatibility between the polymerizable compound as printing ink solvent and gellant is critically important.
In employing existing gellant UV curable ink, this stability insufficient or due to gelling
The addition of agent too much makes curable (patience of image film) insufficient.The present inventor etc. find can be comprehensive
Improve the system of these problems.About this system, enter further in the item of polymerizable compound described later
Row explanation.
To the compound that the ink composite being preferably used in the present invention can be made reversibly to carry out gelation
For example, preferably enumerate: stearone (18-pentatriacontanone), palmitone, 12-23
The fatty acid alcohol such as alkanone, UNILIN425, fatty acid ester, stearic acid inulin fatty acid dextrin (Rheopearl
Series, can obtain from Chiba powder process), Pidolidone derivant (can be from aginomoto Fine-Techno company
Obtain), fatty acid amide (FATTY AMID series, can obtain from KAO. Corp. SA), mountainAcid eicosane
Acid glyceride (Nomukoto HK-G, day clear oillio), jojoba ester (Floraester70, can be from Ikeda thing
Product company obtains), Japanese Unexamined Patent Publication 2005-126507, described in Japanese Unexamined Patent Publication 2005-255821
The oil gellant equimolecular quantity low molecular compound less than 1000, but it is not limited to this.
It addition, the example of fatty acid amide has FATTY AMID E: erucyl amide, FATTY AMID
T: oleamide, FATTY AMID O-N: solidification tallow fatty acid amide (can obtain from KAO. Corp. SA above),
Nikkaamaido AP1: stearic amide (can obtain from chemical conversion company of Japan), GP-1:N-lauroyl-L-
Glutamic acid dibutyl amide (can obtain from aginomoto Fine-Techno company) etc..
Example in the present invention, from the viewpoint of gelatinisation ability, to the gellant that can particularly preferably use
For son, the compound shown in following formula (G1) and (G2) can be enumerated.
Formula (G1): R1-CO-R2
Formula (G2): R3-COO-R4
[in formula, R1～R4Represent and separately represent that there is the linear fraction that carbon number is 3～36,
And can have the alkyl chain of side chain]
These gellant can more stable (repeatability is good) suppress the merging of ink dot.
It addition, linking part has amide groups, the fatty acid amide ammonia of the higher group of urethano isopolarity
Ester compounds, at the end of the alkyl chain that carbon number is 3～36, there is-OH ,-COOH isopolarity base
The compound etc. of group is preferred embodiment in known example, is commonly used for gellant.But, the present invention
People etc. find, these compounds not only poor stability in the ink of heated condition (separate out, layer separates),
And cause the dissolution gellant image film after UV solidifies lentamente, preserve bar at some image
Problem can be become under part.
For the example of preferred gellant, the compound described in table 1 below can be enumerated, but
It is not limited to this.
[table 1]
The gellant of the active ray-curable inkjet ink of the present invention from ink jet recording head spray after, if
Land on the recording materials that temperature is lower than gelling temperature, then due to ink temperature reduce be carved into for thirty years of age into
Gel state.By forming gel state, ink dot mixing each other, the merging of ink dot can be suppressed, can be
High image quality is formed during high speed printing.Then, solidify by irradiating active ray, be consequently formed fixing
Firm image film on recording materials.
The content of gellant is preferably 2～10 mass %, more preferably 3～7 mass %.If less than 2
Quality %, then gel formation is insufficient, it is impossible to completely inhibit the merging of ink dot, if it addition, more than 10 matter
Amount %, then the problem that after there is active ray irradiation, curable deteriorates.
(polymerizable compound)
The jetted ink of the present invention contains (A) molecular weight 300～1500, has 3～14 in intramolecular
(-CH2-CH2-O-) shown in (methyl) acrylate compounds of construction unit (hereinafter also referred to as " polymerism
Compound A ") and (B) molecular weight 300～1500, ClogP value (methyl) third in the range of 4.0～7.0
Enoic acid ester compounds (hereinafter also referred to as " polymerizable compound B ") is as photopolymerizable compound.
As it has been described above, in the UV curable ink employing existing gellant, not to gellant and work
Studying in detail for the compatibility between the polymerizable compound of solvent, the printing initial stage can suppress ink dot
Merge, if but continue printing, become unstable or any of the above-described performance degradation and each performance cannot be taken into account.
The present inventor etc. find first, in the active ray-curable inkjet ink employing above-mentioned gellant,
In order to meet good curable, there is no cure shrinkage (resistance to bend(ing) is good), guarantee high image quality (suppression ink
Point merges, does not has word to obscure) these all will repeatability (gellant steady dissolution=ejection stability)
Ask, need to be applied in combination polymerizable compound A and polymerizable compound B with mass range described later.
The molecular weight of polymerizable compound is preferably in the range of 300～1500.There is molecular weight less than 300
Polymerizable compound and gellant ink composite due to ejection temperature before and after ink viscosity changed
Greatly, accordingly, it is difficult to maintain the temperature of ink composite so that from the ejection optimization of inkjet head.It addition,
There is the ink composite of the molecular weight polymerizable compound gellant more than 1500 due to oil after solation
Ink viscosity is the highest, and the compositions accordingly, as jetted ink is improper.It addition, by selecting molecule
The polymerizable compound of amount more than 300, can eliminate the existing oil containing free-radical polymerised compound
The problems such as the abnormal smells from the patient becoming the abnormal smells from the patient of ink of problem itself, printed article in ink.
In polymerizable compound A, if (-CH2-CH2-O-) shown in construction unit number less than 3, then solid
Change and shrink greatly, printed article can be made to crimp.On the other hand, if said structure unit number is more than 14, the most not only
Molecule quantitative change cannot be carried out greatly stable ejection, and gellant dissolubility also deteriorates and makes ejection unstable.
3～14 construction units can be interconnected, it is also possible to is separately present dividing in polymerizable compound A
In son.In a word, as long as at the molecular memory of polymerizable compound A at 3～14 (-CH2-CH2-O-) institute
The construction unit quantity shown.
The content of polymerizable compound A is preferably in the range of 30～70 mass % of ink entirety.If it is low
In 30 mass %, then cure shrinkage is big, printed article can be made to crimp, make image film ftracture during curved images.
On the other hand, if more than 70 mass %, then improve due to the hydrophilic that ink is overall, meet above-mentioned gel
The gellant changing important document cannot stably dissolve in ink, it is impossible to is stably formed high resolution image.
For the example of (methyl) acrylate compounds of polymerizable compound A, can enumerate following
Compound, but be not limited to this.
Saretomer company manufacture 4EO modification hexanediyl ester CD561 (molecular weight 358),
3EO modification trimethylolpropane trimethacrylate SR454 (molecular weight 429), 6EO modification trihydroxy methyl third
Alkane triacrylate SR499 (molecular weight 560), 4EO modification tetramethylol methane tetraacrylate SR494 (molecule
Amount 528), polyethyleneglycol diacrylate NK ester A-400 (molecular weight 508) of chemical company of Xin Zhong village,
NK ester A-600 (molecular weight 742), polyethylene glycol dimethacrylate NK ester 9G (molecular weight 536),
NK ester 14G (molecular weight 770), the tetraethylene glycol diacrylate that Osaka organic chemistry company manufactures
The trimethylolpropane EO modified triacrylate that V#335HP (molecular weight 302), Miwon company manufacture
Miramer M3160 (molecular weight 560), tetramethylolmethane EO modification tetraacrylate Miramer
M4004 (molecular weight 572).
In polymerizable compound B, only it is being less than, by ClogP, the feelings that the polymerizable compound of 4.0 is constituted
Under condition, ink entirety described above becomes hydrophilic, and the dissolubility of gellant, stability are difficult to ensure that.
If it addition, use the ClogP polymerizable compound more than 7.0, then light trigger, the dissolving of initiation auxiliary agent
Property, stability are difficult to ensure that, cause that curable is bad, it is bad to spray.
The content of polymerizable compound B is preferably in the range of 10～40 mass % of ink entirety.If it is low
In 10 mass %, then ink entirety becomes hydrophilic, the dissolubility of gellant, poor stability.If exceeding
40 mass %, then cure shrinkage is big, printed article can be made to crimp, make image film ftracture during curved images.Again
Person, from the viewpoint of maintaining curable and suppression cure shrinkage, preferred polymeric compound B is to divide
There are in son 3～14 (-C (CH3)H-CH2-O-) shown in construction unit trifunctional more than methyl-prop
Olefin(e) acid ester or acrylate compounds or there is the first of more than two senses of circulus in intramolecular
Base acrylate or acrylate compounds.It addition, from the standpoint of repeatability improves further,
And, from being concatenated to form gel, from the standpoint of improving repeatability further, particularly preferably.
3～14 construction units can be interconnected, it is also possible to is separately present dividing in polymerizable compound A
In son.In a word, as long as at the molecular memory of polymerizable compound B at 3～14 (-C (CH3)H-CH2-O-)
Shown construction unit quantity.
For the example of (methyl) acrylate compounds of polymerizable compound B, can enumerate following
Compound, but be not limited to this.
The 3PO modification trimethylolpropane trimethacrylate Photomer4072 that Cognis company manufactures (divides
Son amount 471, ClogP4.90), the decamethylene-glycol dimethylacrylate that chemical company of Xin Zhong village manufactures
NK ester DOD-N (molecular weight 310, ClogP5.75), Tricyclodecane Dimethanol diacrylate NK ester
A-DCP (molecular weight 304, ClogP4.69) and Tricyclodecane Dimethanol diacrylate NK ester
DCP (molecular weight 332, ClogP5.12).
The present invention is realized by using the active ray-curable inkjet ink of the present invention within the above range
The reason of effect does not the most determine, such as, be considered following reason.That is, in the jetted ink of the present invention,
Polymerizable compound A that hydrophilic the is higher and higher polymerizable compound B of hydrophobicity is high in uniformity
Mixing under state, the gellant with hydrophobic parts and hydrophilic parts can remain higher
Stably it is present in these polymerizable composition, polymerizable compositions while uniformity.And think, thus, can stablize
And promptly carry out collosol and gel, therefore, it can carry out the stable ejection of ink, and can effective ground resistance
The only unification of ink.
The polymerizable compound of the present invention is applied in combination polymerizable compound A and polymerizable compound B, can
To use known all (methyl) acrylate monomers and/or oligomer.Described in the present invention " with/
Or " refer to can be monomer, it is also possible to for oligomer, it is also possible to containing both meanings.It addition, with
The content of lower narration also means this.
The example of monofunctional monomer includes: isoamyl acrylate, stearyl acrylate ester, lauryl acrylate,
The different myristin of 1-Octyl acrylate, decyl acrylate, acrylic acid, the different stearyl ester of acrylic acid, 2-ethyl hexyl
Base-diethylene glycol acrylate, acrylic acid 2-hydroxybutyl, hexahydrophthalic acid 2-acryloyloxyethyl ester,
Acrylate, butoxy ethyl, ethoxydiglycol acrylate, methoxyl group diethylene glycol acrylate,
Methoxy polyethylene glycol acrylate, MPEG 2-methoxy-propane-1,3-diol. acrylate, acrylate, third
Olefin(e) acid tetrahydro furfuryl ester, isobornyl acrylate, acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester,
2-hydroxyl-3-phenoxypropylacrylate, succinic acid 2-acryloyloxyethyl ester, phthalic acid 2-third
Alkene acyloxy ethyl ester, phthalic acid 2-acryloyl-oxyethyl-2-hydroxy methacrylate, lactone-modified flexible third
Olefin(e) acid ester, t-butylcyclohexyl ester etc..
The example of 2 functional monomers includes: triethylene glycol diacrylate, tetraethylene glycol diacrylate, poly-
Glycol diacrylate, tripropylene glycol diacrylate, polypropyleneglycol diacrylate, 1,4-butanediol
Diacrylate, 1,6 hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol dipropyl
Olefin(e) acid ester, dihydroxymethyl tristane diacrylate, the PO addition product diacrylate of bisphenol-A,
3-hydroxypivalic acid neopentylglycol diacrylate, polytetramethylene glycol diacrylate etc..
3 officials can the example of above polyfunctional monomer include: trimethylolpropane trimethacrylate, season penta
Tetrol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, two (three hydroxyl first
Base propane) tetraacrylate, glycerol propoxylate, caprolactone modification trimethylolpropane tris third
Olefin(e) acid ester, tetramethylolmethane ethyoxyl tetraacrylate, caprolactam modification dipentaerythritol acrylate
Deng.
Additionally, polyreactive oligomers class also can coordinate in the same manner as monomer.Example to polyreactive oligomers
For, can enumerate epoxy acrylate, aliphatic urethane acrylate, aromatic series urethane acrylate,
Polyester acrylate, straight acrylic oligomer etc..
It addition, see from sensitivity, skin irritation, eye irritation, mutagenicity (originality), toxicity etc.
Point considers, in above-mentioned monomer, and particularly preferred isoamyl acrylate, stearyl acrylate ester, lauryl
The different myristin of ester, 1-Octyl acrylate, decyl acrylate, acrylic acid, the different stearyl ester of acrylic acid, ethoxy
Base diethylene glycol acrylate, methoxy polyethylene glycol acrylate, MPEG 2-methoxy-propane-1,3-diol. acrylate,
Isobornyl acrylate, lactone-modified flexible acrylic's ester, tetraethylene glycol diacrylate, Polyethylene Glycol
Diacrylate, polypropyleneglycol diacrylate, dipentaerythritol acrylate, two (trihydroxy methyls third
Alkane) tetraacrylate, glycerol propoxylate, caprolactone modification trimethylolpropane tris acrylic acid
Ester, tetramethylolmethane ethyoxyl tetraacrylate, caprolactam modification dipentaerythritol acrylate.
Wherein, more particularly preferably stearyl acrylate ester, lauryl acrylate, the different stearyl ester of acrylic acid,
Ethoxydiglycol acrylate, isobornyl acrylate, tetraethylene glycol diacrylate, glycerol third
Epoxide triacrylate, caprolactone modification trimethylolpropane trimethacrylate, caprolactone modification two season penta
Tetrol six acrylate.
(light trigger)
The light trigger of the present invention can cause the polymerization of polymerizable compound by light.The example of light trigger
Son, it is possible to use " application of UV EB curing technology and market " (CMC publishes, Tian meter Sui supervises
/ Radtech research association edits) etc. in all known optical free radical initiator published.Such as can make
With aryl alkyl ketone, oximinoketone, S-phenyl thiobenzoate, titanocenes, aromatic ketone, thiaxanthone, benzene
Even acyl and the known optical free radical propellant such as quinoline, coumarin ketone.
Wherein, from the standpoint of sensitivity, preferably use acylphosphine oxide and acyl phosphate.
Specifically, the most double (2,4,6-trimethylbenzoyl) phenyl phosphine oxides, double (2,6-dimethoxys
Benzoyl)-2,4,4-trimethylpentylphosphine oxide etc..
The content of light trigger is preferably the scope of 1～10 overall mass % of ink composite, more preferably
The scope of 2～8 mass %.
(colorant)
The colorant of the active ray-curable inkjet ink that can be used for the present invention preferably comprises various known
Dyestuff and/or pigment, particularly preferably contain pigment.
It is exemplified below the pigment preferably used in the present invention.
C.I. pigment yellow 1,2,3,12,13,14,16,17,73,74,75,81,83,87,
93,95,97,98,109,114,120,128,129,138,150,151,154,155,
180,185,213
C.I. paratonere 5,7,12,22,38,48:1,48:2,48:4,49:1,53:1,57:1,63:1,
101,112,122,123,144,146,168,184,185,202
C.I. pigment violet 19,23
C.I. pigment blue 1,2,3,15:1,15:2,15:3,15:4,18,22,27,29,60
C.I. pigment Green 7,36
C.I. Pigment white 6,18,21
C.I. pigment black 7
The dispersion of above-mentioned pigment such as can use ball mill, sand mill, grater, roller mill, blender,
Henschel mixer, colloid mill, ultrasonic homogenizer, ball mill, wet shotcrete technology film machine, paint stirring
Device etc..
During it addition, carry out pigment dispersion, it is also possible to add dispersant.The example of dispersant is preferably used height
Dispersal agent molecule, for the example of macromolecule dispersing agent, can enumerate, the Solsperse of Avecia company
The PB series of series and aginomoto Fine-Techno company.
It addition, as dispersing aid, it is possible to use the synergist of corresponding various pigment.These dispersants
And dispersing aid adds 1～50 mass parts preferably with respect to pigment 100 mass parts.Disperse medium uses solvent
Or polymerizable compound is carried out, but in the illuminated line curable ink of the present invention, due at ink
Just will be allowed to after land carry out reaction solidification, it is therefore preferable that be solvent-free.If dissolvent residual is solid
Change in image, then the problem producing the VOC of the deterioration of solvent resistance, residual solvent.It is therefore preferable that point
Dispersion media is not solvent, but polymerizable compound, wherein, preferably select viscous in terms of Bet-hedging
Spend minimum monomer.
The mean diameter of the dispersion preferred pigments particle of pigment is 0.08～0.2 μm, and maximum particle diameter is
0.3～10 μm, preferably 0.3～3 μm.In order to be adjusted the mean diameter of pigment, suitably select pigment,
Dispersant, disperse medium, suitably set dispersion condition, filtercondition.Managed by this particle diameter, can press down
The blocking of spray nozzle processed, maintains the storage stability of ink, the ink transparency and solidification sensitivity.
It addition, the active ray-curable inkjet ink of the present invention can use existing known as required
Dyestuff, is preferably used oil-soluble dyes.The example of the oil-soluble dyes that can use in the present invention comprise with
Under material, but be not limited to this.
(rosaniline dyes)
MS Magenta VP, MS Magenta HM-1450, MS Magenta HSo-147 (are three above
Jing Dong pressure company system), AIZENSOT Red-1, AIZEN SOT Red-2, AIZEN SOTRed-3,
AIZEN SOT Pink-1, SPIRON Red GEH SPECIAL (being hodogaya chemical company system above),
RESOLIN Red FB200%, MACROLEX Red Violet R, MACROLEX ROT5B (with
Upper for Bayer Japan company system), KAYASET Red B, KAYASET Red130, KAYASET
Red802 (being chemical medicine company of Japan system above), PHLOXIN, ROSE BENGAL, ACID Red (with
Upper for Daiwa chemical conversion company system), HSR-31, DIARESIN Red K (being melted into society's system for Rhizoma Sparganii above),
Oil Red (BASF Japan company system).
(cyanine dye)
MS Cyan HM-1238, MS Cyan HSo-16, Cyan HSo-144, MS Cyan VPG (with
On be three Jing Dong pressure company systems), AIZEN SOT Blue-4 (hodogaya chemical company system), RESOLIN
BR.Blue BGLN200%、MACROLEX Blue RR、CERES Blue GN、SIRIUS
SUPRATURQ.Blue Z-BGL, SIRIUS SUPRA TURQ.Blue FB-LL330% (are above
Bayer Japan company system), KAYASET Blue FR, KAYASET Blue N, KAYASET Blue
814, Turq.Blue GL-5200, Light Blue BGL-5200 (be above Japanese chemical medicine company system),
DAIWA Blue7000, Oleosol Fast Blue GL (being melted into company's system for Daiwa above),
DIARESIN Blue P (Rhizoma Sparganii chemical conversion company system), SUDAN Blue670, NEOPEN Blue808,
ZAPON Blue806 (be above BASF Japan company system).
(weld)
MS Yellow HSm-41, Yellow KX-7, Yellow EX-27 (three Jing Dong pressures), AIZEN SOT
Yellow-1, AIZEN SOT YelloW-3, AIZEN SOT Yellow-6 (are hodogaya chemical society above
System), MACROLEX Yellow6G, MACROLEX FLUOR.Yellow10GN (be Bayer above
Japan company system), KAYASET Yellow SF-G, KAYASET Yellow2G, KAYASET
Yellow A-G, KAYASET Yellow E-G (being chemical medicine company of Japan system above), DAIWA Yellow
330HB (Daiwa chemical conversion company system), HSY-68 (Rhizoma Sparganii chemical conversion company system), SUDAN Yellow146,
NEOPEN Yellow075 (be above BASF Japan company system).
(black dyes)
MS Black VPC (three Jing Dong press company's system), AIZEN SOT Black-1, AIZEN SOT
Black-5 (being hodogaya chemical company system above), RESORIN Black GSN200%, RESOLIN
BlackBS (be above Bayer Japan company system), KAYASET Black A-N (Japanese chemical medicine company system),
DAIWA Black MSC (Daiwa chemical conversion company system), HSB-202 (Rhizoma Sparganii chemical conversion company system),
NEPTUNE Black X60, NEOPEN Black X58 (be above BASF Japan company system) etc..
Containing in the case of colorant in the ink composite of the present invention, preferably colorant concentration is ink combination
1 mass % of thing entirety～the scope of 10 mass %.If more than 1 mass %, then can get good figure
As quality, if below 10 mass %, then can get suitable ink viscosity during ink injection.It addition,
Coloring agent of more than two kinds can be mixed by the adjustment of color etc. to use in good time.
(recording materials)
Recording materials can be paper, it is also possible to for resin molding.The example of paper comprises coated paper for printing, print
Brush coating paper B, good quality paper etc..It addition, the example of resin molding comprises polyethylene terephthalate
Film and vinyl chloride film etc..
The present invention preferably stream causing adjacent ink dot of appropriateness under the degree that adjacent ink dot will not mix
Flat.Its reason is because image film surface and produces concavo-convex, and image gloss declines.The present inventor etc. find,
By ink land temperature of recording materials when the recording materials is adjusted to the collosol and gel phase in version of ink
In the range of temperature-20～this collosol and gel phase transition temperature-10 DEG C, no matter use which kind of gellant can
Adjust above-mentioned image gloss as described above.
Carry out image gloss adjustment to be adjusted by this temperature, need gellant to be stably present in conduct
In the polymerizable compound of solvent, from this side considerations, the structure of the particularly preferred present invention.
(the ejection condition of ink)
The present invention ink ejection condition from ejection stability from the standpoint of, preferably by ink jet recording head,
Ink flow path and ink are heated to 80～120 DEG C, and spray.
In order to stably spray ink from ink jet recording head, the ink viscosity at a temperature of ejection is needed to exist
Between 7～14mPa s.
(image forming method)
In the image forming method of the present invention, as the irradiation condition of active ray, preferably in ink land
Active ray is irradiated respectively between latter 0.001～1.0 second, more preferably 0.001～0.5 second.
Illustrate making technical scheme more efficiently line recording mode image forming method.
Fig. 1 represents an example of the structure of the major part of ink-jet recording apparatus.Fig. 1 (a) is its side
Figure, Fig. 1 (b) is its top view.
Ink-jet recording apparatus shown in Fig. 1 is referred to as line recording mode, to cover the overall width of recording materials
The ink jet recording head 3 of the mode multiple each color ink of fixed configurations on shower nozzle balladeur train 2.By at these
The lower section of fixing shower nozzle balladeur train 2 carries recording materials and forms image.
The transporting velocity of recording materials is preferably 30～120m/s.The fastest image of transporting velocity forms speed more
Hurry up, therefore preferably, if but transporting velocity is too fast, then and image quality reduces or the photocuring (aftermentioned) of ink becomes
Insufficient.
The ink jet recording head 3 that each color is used in the number of the conveying direction of recording materials according to use
Shower nozzle spray nozzle density and printing time resolution change.Such as, drop amount 2pl to be used,
In the case of the image of the resolution that the shower nozzle of spray nozzle density 360dpi forms 1440dpi, at recording materials
On conveying direction, use 4 ink jet recording heads 3 and be in staggered configuration, thus can form 1440 × 1440dpi
Image.Shower nozzle at drop amount 6pl to be used, spray nozzle density 360dpi forms dividing of 720 × 720dpi
In the case of the image of resolution, use 2 ink jet recording heads 3 and be in staggered configuration, thus can be formed
The image of 720dpi.The dpi of the present invention represents the ink dot number of every 2.54cm.
In the way of covering the overall width of recording materials, metal halide lamp is configured in shower nozzle balladeur train 2 downstream
Or LED1.Ink land utilize this light irradiation ultraviolet after recording materials rapidly, and image is complete
Fixing.
Image can for the preferred high-pressure mercury-vapor lamp of light source irradiated, metal halide lamp, LED etc. after being formed
Send illumination 100mW/cm2The light source of above high illumination UV light.Wherein, electric power is preferably consumed few
LED, but it is not limited to this.
It should be noted that the LED1 in Fig. 1 such as uses Phoseon Technology company to manufacture
395nm, water-cooled LED.
The present invention preferably gushes out formation image with the droplet of drop amount 0.5～2.5pl.By by drop amount
It is set to above-mentioned scope, can form the image of fine, and the concavo-convex problem of above-mentioned image film is also subtracted
Gently.But, in the case of the droplet spraying above-mentioned scope, if the poor stability of ink, then cannot
Realize image to be formed.From this side considerations, the ink stability of technical scheme is the best, i.e.
Make the droplet ejection with drop amount 0.5～2.5pl the most no problem, the figure of fine can be stably formed
Picture.
Embodiment
Below, enumerate embodiment and the present invention is specifically illustrated, but embodiments of the present invention are not
It is defined in these examples.
" preparation of dispersible pigment dispersion "
Pigment is disperseed by below step.Following two kinds of compounds are put into rustless steel beaker, at 65 DEG C
Heating plate on heat while heated and stirred makes it dissolve in 1 hour.
AJISPER PB8249 mass parts
Tripropylene glycol diacrylate (manufacture of chemical company of APG-200, Xin Zhong village) 71 mass parts
It should be noted that the preparation of the dispersible pigment dispersion of following ink composition 8 is with being equivalent to polymerism
The acrylate monomer of compound A i.e. CD561 (Sartomer Company manufacture) replaces carrying out APG-200.
After being cooled to room temperature, add following pigment 20 mass parts wherein, with 200g diameter 0.5mm's
Zirconium oxide bead is together put into vial and seals, after painting the dispersion process that agitator carries out the following time,
Remove zirconium oxide bead.
Dispersible pigment dispersion 1: pigment black 7 (Mitsubishi Chemical Ind's manufacture, #52) 5 hours
Dispersible pigment dispersion 2: pigment blue 15: 4 (refine big day manufacture, CHROMOFINE BLUE6332JC)
5 hours
Dispersible pigment dispersion 3: pigment yellow 150 (manufacture of LANXESS company, E4GN-GT CH20015) 8
Hour
Dispersible pigment dispersion 4: pigment red 122 (refine big day manufacture, CHROMOFINE RED6112JC)
8 hours
" preparation of ink composite "
Ink is prepared in the combination formed with the gellant described in table 1 according to the ink described in table 2～30,
Prepare ink composition 3～31.Then, Teflon (login trade mark) 3 μm manufactured with ADVATEC company
Membrane filter filters the ink composition of preparation.
It should be noted that ink composition 1 (comparing ink) uses the Phaser860 that Xerox company manufactures
With ink, the ink composition 2 following ultraviolet curable ink of use, described ultraviolet curable ink exists
Common ultraviolet curable ink without gellant, U.S. Patent No. 7423072B2 description
The addition of acrylic acid tetrahydro furfuryl ester (is reduced 5%, correspondingly adds 3% by the ink of embodiment prescription 1
Stearyl stearate and 2% distearyl ketone) in containing gellant.
It is as shown in the table for the sol-gel phase transition temperature of each ink.It should be noted that sol-gel turns mutually
Determination of viscoelasticity device MCR300, shear rate 11 (1/s) that temperature Physica company manufactures are entered
Row measures.
[table 2]
Remarks: do not have ClogP4.0-7.O acrylate
[table 3]
Remarks: ClogP4.0-7.0 acrylate 8%
[table 4]
Remarks: ClogP4.0-7.0 acrylate 45%
[table 5]
Remarks: ClogP4.0-7.0 acrylate 60%
[table 6]
Remarks: EO modification acrylate 20%, ClogP4.0-7.0 acrylate lO-40%
[table 7]
Remarks: replace APG-200 to disperse with CD561
EO modification acrylate 70%, cIogP4.0-7.0 acrylate 10-40%
[table 8]
Remarks: gelating agent 1%
[table 9]
Remarks: gelating agent 15%
[table 10]
[table 11]
[table 12]
[table 13]
[table 14]
[table 15]
[table 16]
[table 17]
[table 18]
[table l9]
[table 20]
[table 21]
[table 22]
[table 23]
[table 24]
[table 25]
[table 26]
[table 27]
[table 28]
[table 29]
[table 30]
" method of ink jet image formation "
Each ink composite of above-mentioned preparation is loaded in the ink-jet recording apparatus have ink jet recording head,
This ink jet recording head has piezoelectric type ink-jet nozzle.Use this device to chrysanthemum half-size scale (long 939mm × wide
Coating paper 636mm) (OK topcoat, Oji Paper company manufactures) and good quality paper (OK Prince quality,
Oji Paper company manufactures) carry out 500 image records continuously.The transporting velocity of recording materials is at 30m/s
Carry out with under the conditions of 60m/s the two.
Ink supply system though it is not illustrated, its by ink cartridge, supply pipe, before shower nozzle dead ahead
Room ink cartridge (Subinktank), the pipe arrangement of band filter, piezo jets are constituted, from full room box to showerhead
Point carry out heating and carry out 100 DEG C heat.For piezo jets, each color uses four 360dpi
The shower nozzle of resolution, and apply voltage and form the drop of 2pl and spray, form 1440 × 1440dpi
YMCK monochrome image on the spot and RGB secondary colours image on the spot.
After printing, the LED (8W/cm manufactured with Phoseon Technology company2、water cooled
Unit) solidification.(the irradiating width 20mm of conveying direction) is irradiated in the distance away from pipe face 5mm.
" various evaluation "
<gellant steady dissolution>
Use the Y ink that each ink forms, perusal stand 4 hours at 100 DEG C after dissolved form
State.
Zero: do not separate, separate out
×: oil droplet is gathered in surface (layer separation)
<ink stink>
Use the Y ink that each ink forms, evaluate stink when being heated to 100 DEG C.
Zero: stink is little
×: there is strong impulse stink
<image quality (deinking)>
For the image output of each sample, naked eyes confirm 100% when printing the 10th and the 500th
Whether Printing Department does not has blank (the non-printing caused due to the merging of ink dot).
Zero: there is no deinking
△: have deinking at 1,2, but practical no problem
×: produce multiple deinking
<image quality (text quality)>
For the image output of each sample, 3pt when visual valuation prints the 10th and the 500th is bright
Quality towards word.
Zero: reappear
△: see that a part of word obscures
×: word obscures
<image quality (gloss)>
For the OK topcoat paper image output of each sample, measure 100% Printing Department of the 10th
60 degree of gloss numbers.
Zero: 15～60
△: 61～100 and 1～14
(paper, art paper are coated with in a large number for OK topcoat paper etc., the scope of 15～60 and paper in vain it
Between there is no sense of discomfort, the most preferably)
<curable evaluation (pencil hardness)>
About the OK topcoat paper image output of each sample, 100% Printing Department of the 10th is existed
25 DEG C, place 24 hours in the environment of 60%RH after, the pencil measuring surface according to JIS-K-5400 is hard
Degree is also evaluated according to following grade, as one of curable index.
Zero: more than pencil hardness 2H
△: B, F, H
×: below 2B
<bending patience>
About each sample OK topcoat paper export image, 100% Printing Department of the 10th 25 DEG C,
After placing 24 hours in the environment of 60%RH, doubling.
Zero: image film does not rupture
×: in the parts of images film rupture folded
<image preservability>
The image exported about the OK topcoat paper of each sample, 100% Printing Department of the 10th exists
After placing 1 month in the environment of 40 DEG C of 80%RH, naked eyes confirm imaging surface.
Zero: there is no precipitate
△: somewhat have white precipitate
Above-mentioned evaluation result etc. is collected and is shown in table 31, table 32 and table 33.
[table 31]
[table 32]
1:40 DEG C of 80%RH1 of ※ month
Table [33]
40 DEG C of 80%RH1 of ※ months
It is clear that by the result shown in table 32 and table 33, in various evaluations, uses the work of the present invention
Property the image that formed of ray-curable inkjet ink than using, to compare the image that ink formed excellent.
I.e., it is known that, even if method according to the invention it is possible to offer one can also under high-speed record
It is stably formed the image of fine, the active ray-curable good to the adaptability of various recording materials
Jetted ink.It addition, understand, it is possible to provide a kind of image using this active ray-curable inkjet ink
Forming method.
The application is CLAIM OF PRIORITY based on Japanese Patent Application 2011-037973 filed in 24 days February in 2011.
The content that this application description and figure are recorded all quotes present specification.
Industrial utilizability
According to the present invention, it is possible to provide fine can also be stably formed under high-speed record even if a kind of
Image, the active ray-curable inkjet ink good to the adaptability of various recording materials.It addition, can
A kind of image forming method using this active ray-curable inkjet ink is provided.
Symbol description
1 light emitting diode (LED)
2 shower nozzle balladeur trains
3 ink jet recording heads
Claims (6)
1. an active ray-curable inkjet ink, it contains gellant, the first optical polymerism chemical combination
Thing, the second photopolymerization compounds and light trigger, this ink reversibly carries out collosol and gel according to temperature
Phase in version, wherein,
(1) relative to ink total quality, containing the molecular weight in the range of 30～70 mass % 300～1500
In the range of and in intramolecular, there are 3～14 (-CH2-CH2-O-) shown in (methyl) third of construction unit
Enoic acid ester compounds as described first photopolymerizable compound,
(2) quality overall relative to ink, containing the molecular weight in the range of 10～40 mass % 300～
In the range of 1500 and (methyl) the acrylate compounds conduct in the range of 4.0～7.0 of ClogP value
Described second photopolymerizable compound, and,
(3) total carbon atom number of described gellant is more than 12, and containing carbon number be more than 3 straight
Chain or branched alkyl chain,
(4) at least one chemical combination during described gellant is the compound shown in following formula (G1) and (G2)
Thing,
Formula (G1): R1-CO-R2
Formula (G2): R3-COO-R4
In formula, R1～R4Separately represent that there is the linear fraction that carbon number is 3～36, and
Optionally there is the alkyl chain of side chain.
2. active ray-curable inkjet ink as claimed in claim 1, wherein, described activity light
Line curable ink-jet ink is possibly together with colorant.
3. active ray-curable inkjet ink as claimed in claim 1, wherein, described second light
Polymerizable compound is at least one (methyl) acrylate compounds in following (4) and (5),
(4) in intramolecular, there are 3～14 (-C (CH3)H-CH2-O-) shown in construction unit trifunctional with
On (methyl) acrylate compounds,
(5) there is (methyl) acrylate compounds of more than two senses of circulus in intramolecular.
4. active ray-curable inkjet ink as claimed in claim 1 or 2, wherein, described glue
The content of solidifying agent is 2～10 mass %.
5. active ray-curable inkjet ink as claimed in claim 1 or 2, it is used for image shape
Become.
6. an image forming method, it uses the active ray-curable described in claim 1 or 2
Jetted ink, wherein, by described active ray-curable inkjet ink land record material when the recording materials
The temperature of material controls the collosol and gel phase transition temperature for described active ray-curable inkjet ink
In the range of-20 DEG C～this collosol and gel phase transition temperature-10 DEG C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011037973 | 2011-02-24 | ||
| JP2011-037973 | 2011-02-24 | ||
| PCT/JP2012/001245 WO2012114759A1 (en) | 2011-02-24 | 2012-02-23 | Active ray-curable inkjet ink, and image formation method |
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| Publication Number | Publication Date |
|---|---|
| CN103547639A CN103547639A (en) | 2014-01-29 |
| CN103547639B true CN103547639B (en) | 2016-08-17 |
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|---|---|
| US (1) | US8877827B2 (en) |
| EP (1) | EP2679640B1 (en) |
| JP (1) | JP5747312B2 (en) |
| CN (1) | CN103547639B (en) |
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| WO2013150802A1 (en) * | 2012-04-05 | 2013-10-10 | コニカミノルタ株式会社 | Image-forming method |
| CN110981941A (en) | 2013-06-07 | 2020-04-10 | 约翰霍普金斯大学 | Biomimetic peptides and biodegradable delivery platforms |
| US9528013B2 (en) * | 2013-09-09 | 2016-12-27 | Konica Minolta, Inc. | Actinic radiation-curable ink-jet ink and image formation method |
| WO2016013644A1 (en) * | 2014-07-25 | 2016-01-28 | コニカミノルタ株式会社 | Foil image formation method |
| ES2784341T3 (en) * | 2014-12-18 | 2020-09-24 | Canon Production Printing Netherlands B V | Ink composition |
| WO2016125656A1 (en) * | 2015-02-05 | 2016-08-11 | コニカミノルタ株式会社 | Inkjet image formation method |
| JP6572649B2 (en) * | 2015-07-10 | 2019-09-11 | コニカミノルタ株式会社 | Photocurable inkjet ink and image forming method |
| EP3323863B1 (en) * | 2015-07-13 | 2020-06-17 | Konica Minolta, Inc. | Active light ray-curable inkjet ink and inkjet recording method |
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| JPWO2017164164A1 (en) * | 2016-03-22 | 2019-01-31 | コニカミノルタ株式会社 | Image forming method |
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| US8877827B2 (en) | 2014-11-04 |
| US20130335479A1 (en) | 2013-12-19 |
| WO2012114759A1 (en) | 2012-08-30 |
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| CN103547639A (en) | 2014-01-29 |
| JP5747312B2 (en) | 2015-07-15 |
| EP2679640B1 (en) | 2018-11-07 |
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| JPWO2012114759A1 (en) | 2014-07-07 |
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